Process for the low-temperature reduction of iron ores



May 27, 1930. E. D. NEWKIRK r-z- Al. `1,760,078

i PROCESS FOR THE LOW TEMPERATURE REDUCTION OF IRON ORES `Filed Oct. 3. 1927 ffy# zeA

autor nz q Patented May 27, 1930 UNITED STATES PATENT ol-rl'clezv EDGAR D. NEWKIRK AND ARTHUR J'. BRGGS, OF SYRACUSE, NEW YORKv PROCESS FOR THE LOW-TEMPERATURE REDUCTION OF IRON ORES Application led October 3, 1927. Serial No. 223,794.

This invention relates to a process for the reduction of iron ore at relatively low temperatures.

An important object of the invention is to provide a process for the reduction of iron ores which is simple, etiicient and inexpensive.

A further ob]ect of the invention is to provide a process of the character above described by which iron possessing certain superior qualities to that obtained by reduction in blast furnaces may be obtained from its ores.

A further object of the invention is to provide a process by which sponge iron of very high purity is produced from ores by subjecting the ores to relatively low temperatures.

A further object of the invention is to provide a` process for the reduction of iron ore in which the ore, or ore and coke charge is subjected to reducing gases of progressively higher concentration as the charge travels from the entrance end to this discharge end of the furnace or kiln in which the ore is reduced.

A further object of the invention is to pro-4 vide a process for the reduction of iron ores in which the reducing gases employed to accomplish the reduction of the ore, are progressively burned with air, as such reducing gases flow towards the end of the furnace or kiln at which the ore enters, thereby utilizing any surplus reducing gas which may not beI used for reducing the ore in order to provide sufficient temperatures to carry out the reduction reactions.

The ease with which metallic iron can be reduced from its oxide by means of carbon, hydrogen and other reducing agencies at reasonably low temperatures has for years inspired investigation and research in the hope of finding a cheaper and more satisfactory method than now exists for theelementa'- tion of this valuable metal. Further, it seems evident that low temperature reduction retains certain desirable qualities in the iron that are not present in the iron as now reduced by the blast furnaces.

Of the many attempts to reduce iron at low temperatures, there are several that give promise but none has reached the economic position that is possible or necessary iffthis method is to supplant the present blast furnace or reach the position in the art that the improved quality of steel or iron, justifies.

A very pure iron is now being made in Sweden by placing alternate layers of the refined ore and charcoal in a vented sealed container and after heating to about 20009 F. until reaction ceases, it is then cooled without contact with air. When co1d, the charcoal ashes are easily shaken from the frittcd cookies of sponge iron. This gives an cxcellent product but its high cost makes its use very limited.

It has also been demonstrated in a semicommercial Way that when hot hydrogen, carbon monoxide or other reducing gases are assed over iron ore at in the general neighorhood of 1500o F., good grades of sponge iron are produced. This method also is too costly for economic commercial practice.

Of late, semi-successful commercial reduction of iron ore has been accomplished by heating an intimate mixture of finely ground ore and coal, the heat being in some cases supplied indirectly by transmission through refractory walls and in others by direct open tiring in a rotary kiln.

In the two latter methods, a mixture of ground coal and ore is fed in the upper end of the kiln and the heat applied at the lower end. The volatiles of the coal are driven off and move out of the system before thecharge comes to the temperature required for the deoxidation of the ore, and the reduced iron before being discharged from the kiln is subjected to the oxidizing influence of the heating flame.

As will later appear, all of these methods are commercially impractical because of their failure to supply the full chemical and metallurgical requirements of the reactions involved.

lVithin the last few years, it has come to be recognized that the solid phase reactions between carbon and iron ore occur but in a minor degree when reducing gases are present. For, if at atmospheric pressure both CO and-C are present in 'the system, over 90% of the iron oxide will be reduced throuo'h the agency of the gas phase reaction of C5, and less than 10% of the iron oxide will be reduced by carbon in the solid phase.

The gas hase reducing reactions of a mixture of car on and iron ore, when heated to proper temperature are shown by the following equations:

(1) 3Fe2o. Co

2Fe304 COM+ Call.

The sum of these two reactions may be considered as representing the first stage of the reduction and may be written:

To complete the reduction the following reaction takes place.

The CO2 produced, coming in contact with the heated carbon reacts to form double its volume of CO.

Hydrogen reacts similarly, the sum of the reactions being:

3Fe203 'l' 9112-) 6Fe 9II2O 68,400 Cal. (7) 9R20 Sao-anu2 eoo 263,700 Cal.

(8) H2 FeOHnO Fe (9) CO FeOT-COz Fe Kl 8.1 at F.

In the equations, p represents partial pressure and K represents` the equilibrium constant of the reaction.

Thus it will be readily understood that in the reduction of FeO to Fe by CO, as shown in Equation 9, the partial pressure of CO in the reducing gas must be greater than .8 of an atmosphere when the sum of the 00+ CO2 partial pressures equals one atmosphere if the temperature of the ore reducing kiln be 1800o F., in `order to have the reaction proceed as indicated by the upper arrow. If the partial pressure of CO in the reducing gas be less than .8 of an atmosphere, the reaction will proceed as indicated by the lower arrow, thus oxidizing Fe to FeO. From', this it will be seen that in order to completely carry out the reduction of Fe() to Fe by CO, the partial pressure of CO in the reducing gas must be greater than .8 of an atmosphere. Stated differently, the concentration of CO in the .reducing gas, must be greater than 80 per cent.

These constants for the reduction of FeaOi to FeO are seen to be considerably smaller as indicated below.

H2 'l FeaOd-XHZO "l These constants are given for the purpose of showing the relative concentration of reacting gases required in the two principal stages of the process.

In the CO Fe2 O3 CO2 Fe reversible system, it appears that reduction takes place in three stages, each stage becoming substantially complete `before the next stage is begun as indicated by Equations 1, 2 and 4; that a low concentration of the reducing gases in this system will complete the first sta e (Equation 1) that a higher ratio of CO/OZ is required for the second stage Equation 2), and that finally the last stage Equation 4) requires at 1800o F. a partial pressure of the CO in the ratio of .8 atmosypheres where the sum of the partial pressures of the CO and CO2 equal 1 atmosphere. Under these conditions about 95% reduction of the ore to metallic iron may be expected. If a higher degree of deoxidation of the ore is required, correspondingly higher partial pressures of CO are required at the p'oint where the highest degree of elementation of the iron takes place.

ico

-At 1650". F. the reduction of FeO apparently ceases when the ratio of (lO/CO2 falls below .72/.28. Below this ratio iron is reoxidized, notwithstanding the fact that there may be no free oxygen in the system.

Since the amount of CO, irrespective of p its concentration, required to reduce a unit of iron from Fe203 to Fe() is 1/2 the amount required to reduce a similar .unit from F e0 to Fe (Equations 3 and 4) it follows thatat 16.50 F. the ratio of the CO/CCZ gases discharged from the system under ideal coun# ter'current movement of the factors, will be tration is 1 atmosphere.

fronr the system, we utilize b fractionally vburning same-with .air in o r er to furnish the heat required in reducing the CO2 (which about .58 /A provided the initial CO concen- This combustible gas which would normally 'be discharged hasl been Aformed in the process of reducing the ore) to CO (Equation 5) as the former gas reacts with the hot carbon present in the system.

Therefore, ments, it follows that economy in ore reduction indicates acounter current movement of the ore and reducing gases; that low concentration of reducing gases will start the reduction of the ore; that progressively higher CO/ CO2 ratios are required as the reduction of the ore proceeds, and that nally 'the highest concentrations of the reducing gases are necessary, at the deoxidation takes place. l

When ore' is mixed -with solid redu ing agents such as carbon, coal or coke, t ese equilibria hold and the function of the solid point where final reducin agent in' any case, is that of reaction wit the CO2 substantially at the time it is formed to yield double volumes of CO (Equation 5) or to similarly react with water vapor to yie d H2 and CO (Equation 7 ).v

The increase in volume o the CO and the reduction of available O2 held in solid phase by the ore, favor the increase ,Lof reducing gas concentrations within thereaction bed,

as the ore approaches deoxidation.

If the reaction mass is surrounded by an atmosphere of low CO concentration, the development of the required CO concentration within the reaction mass 'is hindered by reason ofthe diffusion of the CO to re ions of lower CO concentration. The rate o diffusion being proportional to the relative difference in degree of concentration existing in the two parts of the system. n I

Since all sta es of ore reduction byCQ yield CO2 whic in turn is reduced by the carbon to CO absorbing heat in the process (Equation 5) it follows that heavy .thermal absorption takes place where the reduction of the-ore is most rapid. Under favorable temperature conditions, this would obviously be during the early stages of reduction where -the oxygen heldxby theore is. in heavy con-V centration. l It follows that to allow' this COv to escape from the system without being reoxidized to CO2, either by the iron oxide or in the production of useful heat applied where the system demands heavy thermal input, would result in low thermal and over all eiiciency, as well as to limit the speed of the: reducing reaction and the degree to which the iron oxide maybe reduced. Itis, there-` fore, apparent' that in order to maintain reav sourl bly uniform temperatures throughout the;reaction4 zone, heat should applied to from the equilibrium requirei the system at the places and in such amounts as the heat absorptio- .s occur.

The present practice of burnin fuel in. contact with the reduced ore at the ower end of the kiln `for the purpose of supplying heat to the reactin mass well within .the interior of the kiln is ound to reoxidize the iron for in studying the equilibrium constants of the reversible reactions co Feo lC02 Fe We find that a so called neutral flame at 1800 F. is decidedly oxidizing to iron. Attempts to make the heating flame reducin enough to prevent reoxidation of the reduce iron result in inadequate temperatures and poor economy. v

Anot er disadvantage of this method of heating, as usually employed lies inthe fact that when all the heating is done Within a relatively short zone at the discharge end of the kiln, not only does local overheating oecur, but the heat is a plied at a point remote from the zone of eav -thermal ;requirc ments, and it becomes di cult to obtain even l. An increasing concentration of reducing gases as the ore approaches complete deoxidation.

2. Provision for continously creating the:

necessary concentrations .of` the reducing gases.

3. Prevention in the fullest degreeof the diilz'usion of the reducing `gases away from contact with the iron oxlde as the latter is` being reduced.

4. The burning @f the-'Cona us-,d in the- `reduction of ore to furnish useful heat where heavy thermal input is required. y

,5. Abilit to maintain and control tem- '.peratures t roughout the reduction zone.

So far as we know, no existing methods provided for the fulfillment of all these requirements and tol meet these/conditions in a workable' and practical manner is the aim and result of our invention.

Inourfinvention, we use an internally fired rotary kilndisposed slightly from the horizontal s o that, the ore, or ore. and coke, or .ore and coal mixture entering one end, gradually moves throughout the length of the kiln i fmv and is discharged at the lower end. For purposes of economy, we refer to use a charge-of iron ore and ow ered low grade,` very friable-coke. Hot 'ghly red tact with the iron in its reduced condition.

` Successively as the thermalrequirements of the reaction', and radiation require, air is admitted at intervals but only in suient required degree of temperature can be main- Y eliminate any tendency reduced and tained over a long Section of the kiln without danger of local overheating.

Another important feature of our process 1s that such CO as may be gene-rated within the reaction bed and escapes therefrom, is

added to the heating gases and there becomes oxidized by the incoming air. The heatthus liberated ecomes available to satisfy the heat absorptions of the reducing reactions.

The advantage of this procedure becomes obvious from the study of the equilibria controlling this process. By this means, we maintain the atmosphere surrounding thereduced iron near the dischar e endv of the furnace or kiln in a highly re retard the CO migration from withinthe reaction bed and leffectively and completely toward sintering or reoxidation. Further advantages are-economy of fuel, easy. temperature control, ability to deliver heat Where, and as the endothermic requirements of the reducing reactlons demand, complete reduction of the ore, no reoxidation of the ore after it has been provision Ifor obtaining suitable temperatures throughout a long section of the kiln, thereby permitting more rapid ore movement therethrough.

In the drawings wherein we have shown a preferred form of apparatus for reducing iron ores in accordance with the method'den scribed above.

Figure 1 is a longitudinal section of the api paratus employed,

Figure 2 shows in elevation the discharge end of the kiln, and,

Figure 3 'is a transverse sectional view taken on line 3 3 of Figure 1.

Referring to the drawings,numeral 10 designates a rotary furnace or kiln which is lined with refractory material such as {ire-brick 11. The lining used in the rotary kiln l0 fmay be either acid, basic or neutral.

The rotary kiln 10 is disposed at a..slight angle to the horizontal, preferably at about a 5 angle, with the end of the kiln at which ueing gases enter at the low end and there come in conucing condition,

ing applied to the supporting wheels. At the right hand end of the kiln as shown in F igure 1 is a stack y14 and also a hopper 15 through which' the lcharge of iron ore or mixture of ore and coke, is introduced into'the rotary kiln. At the opposite, or discharge end of the kiln is a. nonrotative end member 16 which forms a gas tight connection by contacting with the face of the tire 13. This nonrotative end mem-ber is supported by means of depending'arms or rods 17 and 18 from a support 19 which extends transversely of and above the kiln .at a point which is.

is mounted l spaced inwardly from its discharge end. Thev .arms 17 and 18 are liexibly mounted at their upper ends on the support 19, and at their lower ends engage trunnions 17 and 18 re spectively. -By this means', the non-rotative end member 16 maymove, in` any direc-tion except that of rotation as the rotating kiln expands or contracts, and at the same time maintain a gas tight connection between the non-rotatable end member'and the rotating kiln. The end member `16 preferably is provided with a water jacketed annular rim 20 which may be supplied .with water or other cooling Huid to prevent, burning out the rim and also' to maintain thev heavy grease which' is used between the rim 20 and the side of the tire 13 at proper temperature.

Mounted on the rotative kiln 10 is an annular wind box 21. This wind box is maintained in spaced relation to the kiln 10 by means of supp shell 23-of the kiln and the inner circumfer-A ence 24 of the wind box 21. vA supply pipe 25 leads from the wind box 21 andextends longitudinally of the kiln, and has a plurality of branchwind pipes 26, I26 and 26" attached at spaced intervals along pipe 25 as shownl in Figure 1. Valves 27 are provided in the connection of the pipes 26, 26 and 26" with pipe 25 so that the amount of air which may be admitted through each of the pipes 26, 26 and 26, may be properly controlled.' .The ends kof the pipes 26, 26- and 26" through which the air is delivered, preferably are bent so that they deliver the air toward the stack ,14, The annular wind box 21 is provided with a nonrotative cover 28 which makes an air tighnt connection with the wind box'. This stationary .cover28 is held in place byl means of a series of springs 29 spaced circumferentially about the kiln, and having one of their ends contacting with the stationary wind box cover 28, and the other o f their ends abutting against an annular stationary support 30 ex# tending around-the kiln 10. 1

A gasproducer designated generally the numeral 3x1 is provided at the discharge orts 22 inserted between the scribed, the kiln is first rotated and brought up to a suitable working temperature by admitting hot gas from the producer through the pipe 32 into the left hand end of the kiln as shown in Figure 1. Air is admitted as ,desired into the kiln through pipes 26, 26', 26, and also through pipe 33 controlled by valve 34. When the kiln has been brought i up to the desired temperature' which is approximately 180()o F. a charge of'iron ore or a mixture of ore and coke is introduced through hopper 15. The charge of ore or coke and ore flows toward the vleft end of the kiln as shown in Figureil, and the reducing gases supplied by the gas producer iow in the opposite direction and exit through the stack14. The charge is reheated as it travels from the entrance end own to a point slightly to the right of the air pipe 26". As

the charge travels to the left of the kiln as shown in Figure 1 itis constantly subjected to reducing gases of successively higher concentrationsuntil it reaches the discharge end of the kiln and is discharged through outlet 35. From here the reduced iron may be conveyed away by' any desired means and separated from tie gangue, the freeing of the product from impurities forming no part of our invention. The product should be kept out of contact with air until it has cooled to prevent oxidation.

The iron so produced is in the form of granular or spongev iron. This sponge iron may be utilized in any desired manner for the production of steel, wrought iron, or other ferrous products. lThe sponge iron produced in accordance with the process herein described, possesses qualities not found in pig iron produced in blast'furnaces.

Although we have describedfin detail the reduction of iron ore, we do not limit our invention thereto as our process is equally applicable to the reduction of ores bearing nickel, copper, and similar metals. If it is desired to produce metals from sulphid ores, it is only necessary to roast such ores in accordance with well known practices to o xidize the metals, and then proceed as described in the reduction of iron ores.

By the term oxid ores as'used in the claims is meant ores which consist normally to a substantial extent of oxids or ores in which the compound or compounds of the metal to be extracted have been converted into an oxid or oxids.

`.While have described in detail the preferred method of practicing our invention and have shown a preferred type of apparatus to be employed in our process, it is to be understood that various changes may be made in the details of rocedure and in the arrangement of parts othe apparatus without departing from the spirit of our invention o'r the scope of the subjoined claims.

We claim:

1. The process of reducing oxid ores of metals comprising subjecting a charge of ore and carbonaeeous material to progressively higher partial lpressures of reducing gases at temperatures favorable to the reduction.

2. The process of reducing oxid ores of metals comprising subjecting a charge of ore f and carbon aceous material to the action of hot reducing gases and progressively partially burning said reducing gases with air during the reduction of said ore.

3. The process of reducing oxid ores of metals comprising subjectinga charge of ore and carbonaceous material to the action of hot reducing gases flowing counter-current- Wise to the direction of travel of the ore, and progressively increasing the partial pressure of the reducing gases as thereduction of the ore proceeds. i

4. The process of reducing oxid o. \s of metals com rising subjecting a mixture of ore and car onaceous material to hot reducing gases flowing counter-current-wise to the movement of the ore, and progressively and fractionally burning said reducing gases with air during the reduction of the ore, the extent of such burning of the reducing gases lrogressively increasing toward the source o the current of ore.

- 5. The process of reducing oxid ores of metals comprising subjecting a stream of ore and carbonaceous material in a kiln to a counter-current movement of hot reducing gases, controlling the temperature therein and throughout by progressively and fractionally burning the reducing gases with air, and preheating the incoming charge of ore -by finally burning with air the reducing gases ihit eseapefrom the ore reducing zone of the 16. The process of reducing' oxid ores of metals comprising subjecting a moving charge of ore and earbonaceous material to a counter-current movement of hot reducing gases of progressively higher partialpressures, and controlling the temperatures throughout the reaction. zone by` progressive- `ly'burning the reducing gases with air.

In testimony whereof we afiix our signa- 

